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CALCIUM  CARBIDE  AS  AN  AGENT  FOR 
REMOVING  PHOSPHOROUS  AND 
SULPHUR  FROM  IRON  AND 
STEEL 


WILLIAM  JAMES  FARRELL,  Jr. 


THESIS 


FOR  THE 


I)  E GHEE  O E B A G H E L O R O E SCIENCE 

IN 

CHEMISTRY 


COLLEGE  OF  LIBEIJAL  ARTS  AND  SCIENCES 

UNIVERSITY  OF  ILLINOIS 


1922 


•7 


; -1 
i i 


v;>iv 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/calciumcarbideasOOfarr 


UNIVERSITY  OF  ILLINOIS 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

W i_l  l_i  ama  s_  _Pa  r r_e  1_1  * _ 

ENTiTLED___C_aliii_.js__Caxgl.d:^__£-ii_ica_J^Sei^w_jCQj:_iic:rj3YJja^_?i2£)_ci'iiQr_ous._. 

A _ ilu  _f  ?_QU.  _ Ir_Qn_  

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF 


Instructor  in  Charge 


Approved  : 


ACTING  HEAD  OF  DEPARTMENT  OF  .GHEMISTRY. 


500263 


'hi: 


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Yh  wmY^dHu^  y w rf3ai^tra?«A'3H'?  ^tmvr  nitr  rn\T  •.  ,ii  >!-*j  or 


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COFTEiTTS 


Page 

Acknov/ledgement 

Introduction  1 

Discussion  2 

Laboratory  V/ork  

ilethods  of  Analysis  9 

Experimental  Work  

Results  of  Analysis  ..,.27 

Summary  of  Results 

General  Summary 29 

Coniolasions  30 

Suggestion^  Eor  further  Work 30 


Bibliography 


. 31 


AGZIT0WLSDGSM3NT 

I wish  to  express  my  sincere  thanks 
to  Dr,  W,  S,  Putnam  for  the  keen  interest 
he  has  shown  towards  this  work,  and  for  the 
untiring  efforts  and  many  helpful  suggest- 
ions he  has  made# 


-1- 

INTRODUCTION 

Solphur  and  phosphorous  are  the  most  harmful  and  most  com- 
mon enemies  of  steel.  It  is  true  that  oxygen  and  nitrogen  produce  j 
detrimental  effects,  hut  v/ith  proper  treatment  this  objection  can  | 

i- 

s 

be  overcome.  Sulphur  occurs  as  ferrous  sulphide  or  as  manganese  \ 
sulphide  and  phosphorous  exists  as  phosphides  of  iron.  Sulphur  is 
equally  as  harmful  in  cast  iron  as  it  is  in  steel,  however,  small  | 
amounts  of  phosphorous,  not  exceeding  O.lO/a,  are  permissable  in 
cast  iron.  Up  to  the  present  time,  no  commercial  process  has 
been  devised  whereby  these  elements  have  been  entirely  removed. 

They  have,  however,  been  reduced  to  a point  as  low  as  0.01  per 
cent,  but  even  this  small  amount  produces  detrimental  effects,  due 
to  segregation  in  certain  parts  of  the  ingot,  which  not  only  cause 
trouble  during  forgiiEg  in  the  case  of  steel,  but  also  produce  red 
shortness  and  coarse  grained  structure  during  easting. 

The  patch  of  metal  in  which  these  segregations  occur  pos- 
sesses all  the  properties  of  very  inferior  steel  or  iron,  although 
the  average  composition  of  the  remainder  of  the  metal  is  excell- 
ent and  an  analysis  of  the  drillings  failed  to  reveal  this  trouble. 

One  of  the  best  methods  for  detecting  a sulphur  segregation 

is  to  obtain  a representative  polished  surface  and  then  press  a 

piece  of  photographic  paper,  previously  soaked  in  hydroch2koric 

acid,  against  this  surface.  If  a sulphur  segregation  is  present 

fumes  of  hydrogen  sulphide  will  be  generated  v;hich  will  produce  a 
brown  stain  upon  the  paper. 


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These  segregations  can  also  he 
detected  hy  taking  a microphotograph 
of  a polished  surface.  An  analysis 
of  the  drillings  may  fail  to  reveal 
sulphur  segregations,  but  the  micro- 
photograph  will  have  an  appearance 
similar  to  that  shown  in  the  accompany-  Microphotograph  Showing 
ing  illustration.  Sulphide  Segregation. 

Discussion, 

The  object  of  this  thesis  work  is  to  devise  a method  where- 
by the  elements  sulphur  and  phosphorous  can  be  entirely  removed 
from  steel  and  cast  iron  by  use  of  calcium  carbide  as  the  removing 
agent.  The  work  on  cast  iron  was  not  taken  up  until  after  several 
tests  had  been  made  on  low  carbon  steel,  and  it  was  found  that  tem- 
peratures required  to  produce  the  desired  fluidity  of  the  molten 
metal  could  not  be  obtained  with  the  types  of  furnaces  at  hand.  An 
electric  furnace  capable  of  producing  temperatures  as  high  as  2000 
degrees  C,  was  being  constructed,  by  lir.  J.  E.  Eritts,  but  due  to 
delay  in  delivery  of  material,  was  not  completed  soon  enough  to  be 
used  for  this  work. 

The  reactions  by  which  the  complete  removal  of  sulphur  and 
phosphorous  was  expected  were: 

J?gS  CuCg  ^ CnS  "|—  Eo  4-  2G 

Part  of  the  calcium  carbide  would  Jirobably  be  oxidized  to  calcium 
oxide  which  would  produce  the  following  reaction: 


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Si’eS  -I-  2CaO  -I-  CaC^  it  2Fq  -j-  3GaS  -h  2G0 
The  phosphorous  was  to  he  removed  by  the  reaotion: 

2P^P  -h  SCaCg  4-  14PeO  ;t  fCaO^P^C^-^-  20Pe 6C0 


I 


I 


The  chief  difficulty  encountered,  however,  is  that  of  over- 
coming the  great  affinity  iron  has  for  these  two  elements,  namely, 
phosphorous  and  sulphur*  Iron  combines  so  readily  with  sulphur  and 
phosphorous  that  it  is  capable  of  uniting  with  these  elements,  when 
brought  into  contact  v/ith  what  are  considered  otherwise  stable  com- 
poftnds*  *It  has  been  shown  tliat  iron  will  decompose  calcium  sul- 
phate according  to  the  reaction: 

CaSQ|^  -h  4Pe  PeS  4-  CaO  4~  3PeO 

furthermore,  nearly  all  fuels  used  in  the  metallurgy  of  iron 
and  steel  contain  variable  amounts  of  sulphur,  which  is  liberated 
as  a gas  and  absorbed  either  directly  or  indirectly  by  the  ferrous 
metal. 


Manganese  is  capable  ocf  taking  up  sulphur  from  iron  sulphide, 
but  this  compound,  manganese  sulphide,  is  soluble  in  both  the  basic 
slag  and  the  metal,  and  segregations  of  manganese  sulphide  are  just 
as  detrimental  to  the  metal  as  those  of  iron  sulphide. 

BecausO  of  the  solubility  of  manganese  sulphide  in  a basic 
hlag,  this  compound  rises  to  the  surface  where  it  can  be  oxidized 
by  the  oxygen  of  the  air  with  which  it  comes  in  contact,  and  is 
converted  into  free  manganese  and  sulphur  dioxide.  The  sulphur 
dioxide  imsses  off  with  the  other  gases,  and  the  manganese  combines 


I 


*The  Basic  Open  Hearth  Process — Bichmann--1911  p.  167 


-4- 


with  more  of  the  sulphur  oontained  in  the  slag  or  metal  according 
to  the  following  reactions: 

Mn  4-  FeS  MnS  4-  Fe 

I4ciS  -I-  0 2 ^ 4~  SQ  2 

l&i  4-  FeS  ^ MnS  4-  Fe,  etc. 

However,  this  reaction  can  never  he  carried  to  a point  of  less 
than  0.01  per  cent  sulphur  due  to  the  reversibility  of  the  reaction 
as  the  sulphur  content  approaches  this  point. 

Various  other  means  of  removing  sulphur  have  been  devised. 
*Saniter  has  proposed  the  use  of  calcium  chloride  in  conjunction 
with  a basic  slag  rich  in  calcium  oxide,  and  made  fluid  by  the 
addition  of  calcium  fluoride,  but  owing  to  the  large  expense  in 
both  time  and  money  this  method  has  never  been  of  commercial  im- 
portance. 

Sulphur  can  be  completely  removed  from  iron  only  when  con- 
verted into  a form  which  is  insoluble  in  the  metal  but  very  soluble 
in  the  slag.  Galeium  sulphide  fulfills  these  conditions,  but 
according  to  *lProf.  Osann,  this  compound  can  be  produced  only  when 
the  slag  is  free  from  metallic  oxides.  Othervdse,  the  calcium 
sulphide  will  be  decomposed  and  metallic  sulphides  formed  accord- 
ing to  the  following  reaction: 

CaS  4-  FeO  ^ FeS  -h  CaO 

The  sulphur  in  the  form  of  iron  sulphide  will  then  be 

*The  Basie  Open  Hearth  Process— Diehmann— 1911  p.l70 
*1  Stahl  und  Sisen — 1908  pp  873  and  1071 


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-5- 


immediately  returned  to  the  metal# 

In  order  to  keep  the  slag  free  from  metallic  oxides,  reduc-  • 
ing  agents  such  as  calcium  carbide  must  he  present  and  for  possi-  [ 
hility  of  the  carbide  free  from  metallic  oxides  very  high  temper- 
atures are  required#  It  is  because  of  the  necessity  of  these  very 
high  temperatures  that  the  Basic  Open  Hearth  process  fails  to 
produce  steel  absolutely  free  from  sulphur  segregations# 

*Br.  Richard  Moldenke  has  stated  that  a new  desulphurizing 
agent  (probably  a potassium  compound)  had  attained  a wide  vogue  in 
Germany#  This  compound,  when  aided  to  the  molten  metal,  contained 
in  a ladle,  produces  a vigorous  reaction,  and  a thin  slag  forms, 
which  can  be  skimmed  off  after  absorption  by  a small  amount  of 
calcium  oxide.  A reduction  to  sulphur  occurred# 

During  recent  years,  experience  with  the  production  of  steel 
in  electric  furnaces  has  apparently  furnished  full  explanation  of 
the  conditions  necessary  for  the  complete  removal  of  sulphur  and 
phosphorous  from  steel# 

*1  Sulphur  may  be  removed  in  electric  furnaces  by  use  of 
calcium  carbide,  after  complete  deoxidation  of  the  metal  and  slag 
according  to  the  following  reactions,  forming  calcium  sulphide, 
Ifiiich  passes  into  the  slag; 

3PeS  4-  EGaO  4-  CaC^  $ SFe  4-  3CaS  4-  ECO 
Very  high  temperatures  are  required  for  this  reaction  and  the  are 
furnace  is  best  adapted  to  produce  the  required  temperature. 

*Ghem  & Met — May  10,iyES  p.  887 

*1  The  Making,  Shaping  and  Treating  of  Steel  Gamp  and  5’rancos 
19E0  p.  286 


-6- 


*Sulphur  can  iDe  removed  by  use  of  silicon  according  to  the 
follcw^ing  reactions:  (l)  FeS -i-  Si  ^ JB’e  -f-  SiS 

(E)  2GaO  -l-  SiS  ^ CaS  ^iOg  Ca 
(3)  Ga -1-  5’eS  ;;  OaS  -i-  S’e 

The  silicon  sulphide  formed  partly  escapes  as  a gas*  If  calcium 
fluoride  is  used  in  place  of  calcium  oxide  for  the  reaction  (2), 
then  the  reactions, 

(4)  2Ga%-l-  2SiS  2CaS  + Si% -h  Si 
id)  2Ca%  ■+■  ES’eS  -1-  Si  ^ 2CaS  4-  Si;^4-  EITe 
vauld  occur,  and  the  resulting  calciuin  hulphide  would  pass  into 
the  deoxidized  batic  slag* 

*1  According  to  S’.  T.  Sisco,  the  desire  to  remove  phosphor- 
ous and  sulphur  in  electric  furnace  processes,  often  results  in 
the  production  of  ingots  full  of  blow  holes*  This  he  says,  is  due 
to  the  fact  that  carbide  slags  saturated  v;ith  calcium  sulphide  lose 
their  effeciency  as  a deoxidizing  agent,  and  high  carbide  slags 
bdcome  saturated  when  they  contain  3*5  per  cent  of  calcium  sulphide. 
^Further  additions  of  calcium  carbide  to  the  slag  as  desulphurizing 
and  dephosphorizing  continues  will  result  in  the  production  of 
metal  containing  only  traces  of  these  elements*  However,  it  must 
be  remembered  that  deoxidation  is  also  desired,  and  therefore, 
during  the  deoxidizing  period  the  slag  must  be  kept  in  a reducing 
condition  v/ith  only  a low  content  of  calcium  sulphide.  If  these 

*Hleetric  2’iirnaces  in  the  Iron  and  Steel  Industry — 
Hodenhauser,  Schoenawa,  Vom  Baur — 1S17  380-382 

*1  Chem  & Met*— Jan*  4,  1922  pp  17-23 


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-7- 


conditions  exist  then  the  calcium  carbide  will  deoxidize  the  molten 
metal  according  to  the  reaction: 

EJ’eO-i-  CaC2  Z CaO -l-  2Ce-l-2  Fe 

The  electric  furnace  is  now  thoroughly  established  and  the 
fact  that  no  impurities  are  introduced  during  operation,  along  v/ith 
the  fact  that  very  high  temperatures  and  complete  refining  condit- 
ions exist,  mako  it  the  ideal  type  of  furnace  used  for  the  man- 
ufacture of  steel, 

PHOSPHOROUS 

This  element,  although  not  as  objectionable  as  sulphur 
should  never  be  present  in  steel  in  amounts  greater  than  0,10  per 
cent,  as  it  tends  to  produce  a coarse  grained  structure  and  seg- 
regate in  spots, 

*As  to  the  removal  of  sulphur,  it  requires  1,89  per  cent  of 
oxygen  for  each  per  cent  of  phosphorous  present  in  order  th  con- 
vert it  into  a fom  insoluble  in  the  metal  but  soluble  in  the  basic 
slag.  Oxidation  can  be  derived  only  from  metallic  oxides  and  not 
from  lime  as  was  previously  supposed.  Phosphorous  can  be  convert- 
ed into  an  insoluble  form  by  the  following  oxidation  reaction: 

8P  -t-  95*e0  4^  P OqUo.  5Pe 
8 9 4 

In  this  form  phosphorous  can  be  removed  from  the  steel,  but  this 
compound  is  easily  attached  by  reducing  agents  and  will  exist  only 
in  os^genous  surroundings, 

*1  According  to  Stoughton,  this  insoluble  phosphorous  com- 
pound exists  as  3Ca0,P^0  and  unless  the  recarborizer  is  added  to 

5 

*Basic  Open  Hearth  Process-  Pichmann  1911  p.l68 
1 The  Metallurgh  of  Iron  and  Steel-  Stoughton  P*  136 


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the  metal  after  it  has  bden  separated  from  the  slag  the  following 
reactions  will  take  place  causing  the  decomposition  of  this  phos- 
phorous compound  and  the  return  of  phosphorous  to  the  metal: 
2(3Ca().P205) -h  5C  ^ SCaO.P^Og -h  5C0 -h  2P 
4(3CaO.PgO^) -h  6Si  S f eCaO.PgO^  ) -h  bSiO^  + 4P 

Therefore,  in  practice  the  recarburizer  is  usually  added  to  the 
metal,  as  it  is  pouring  from  the  furnace* 

*^eoTges  Vi^  states  that  the  relative  oxidizability  of  phos- 
phorous when  Tjresent  in  molten  iron  is  lower  the  higher  the 
temperature  and  that  above  1400  degrees  it  is  less  oxidizable 
than  manganese,  silicon  or  carbon. 


*L'Age  de  fer,  26,  189-191 


-9- 


LABORATORY  V/01^ 

Varioas  samples  of  iron  and  steel  were  treated  with  calcium 
carbide.  Some  of  tliese  samples  before  treatment  with  calcium  car- 
bide were  treated  with  iron  sulphide  and  ferrous  phosphate  to  in- 
crease the  sulphur  and  phosphorous  content* 

The  following  system  of  marking  the  specimens  was  used, 
li’ive  tests  were  made  and  these  tests  were  numbered  from  one  to  five, 
The  original  specimen  was  marked  with  the  number  corresponding  to 
the  test.  Then  the  specimen  which  was  treated  to  increase  the 
sulphur  and  phosphorous  content  was  marked  v/ith  the  number  of  the 
corresponding  test  and  the  letter  ”A”  beside  it.  After  this  high 
sulphur  and  phosphorous  content  sample  had  been  treated  with  oalciui 
carbide  it  was  marked  with  the  corresponding  number  of  the  test  and 
the  letter  "B"  beside  it. 

*Methods  of  Analysis 

Each  sample  was  analized  before  and  after  each  treatment  to 
determine  the  carbon,  pjjosphorous  and  sulphur  content. 

Determination  of  Total  Carbon 

Total  carbon  was  determined  by  direct  combustion  vi/ith  oxygen. 
The  combustion  train  as  shown  in  Eig.  4,  was  used.  The  sample  of 
iron  or  steel  was  placed  in  an  alundum  combustion  boat,  and  this 
combustion  boat  was  placed  in  the  center  of  a quartz  tube,  which 
was  heated  to  a temperature  of  1,000  degrees  Q by  means  of  an 
electric  resistance  furnace.  The  pressure  exerted  by  the  water  con- 

*The  Bxamination  of  Iron,  iteel  and  Brass — Hall  and  Williams 


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ll 


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,'  1 A •;  ■■ 

T’  o ' 

■ ,. ,.  >.*'  . r>'. 


i-  T.'  1*.  0, r**:!  . •'f' 

>_•  ■ ■ ok^'-  ■'•  '‘ipjo 

' >:  <■•  *■  k-  '" 


I.* 


■ASa  V « Vi  «1  WW  tfv*k  • 


1 1 I 


I .h 


1 ^ 4'iisn*‘ 7'r?5si  ^ ^ rf 


li 

■ I 


, (- 
' i 

i 

/.  i 

1 


-10- 


tained  in  the  upper  ei^t  liter  aspirator  bottle  forced  the  oxygen 
out  of  the  lower  aspirator  bottle  and  thru  the  combustion  train* 
Before  coming  into  contact  with  the  Bample  the  oxygen  passed  thru 
a concentrated  sodium  hydroxide  solution  followed  by  concentrated 
sulphuric  acid* 

The  oxygen  then  passed  over  a coil  of  copper  oxide  and  came 
into  ccntaot  with  the  sample  of  steel,  oxidizing  any  carbon  pres- 
ent to  carbon  dioxide*  The  resulting  gases  passed  over  another 
copper  oxide  coil,  then  thru  a concentrated  solution  of  chromic 
acid,  which  removed  any  oxides  of  sulphur  present,  and  into  the 
absorption  tower*  Here  the  carbon  dioxide  reacted  with  the  sodium 
hydroxide  (commercial  lye),  contained  in  this  tower,  forming  sodium 
carbonate  and  water.  The  water  was  absorbed  by  phosphorous  pent- 
oxide  contained  in  the  attached  tube,  and  the  excess  oxygen  passed 
on  thru  the  barium  hydroxide  solution,  causing  the  precipitation 
of  barium  carbonati  if  any  carbon  dioxide  remained  in  the  gas* 

The  absorption  tower  was  weighed  before  and  after  absorption 
of  carbon  dioxide,  and  the  difference  in  weight  gave  the  v/eight  of 
carbon  dioxide  formed  during  combustion.  5*rom  this  weight  and  by 
knowing  the  weight  of  steel  used,  the  percentage  of  carbon  present 
in  the  original  sample  was  calculated. 


*Jour.  Ind.  & 2ng  ^hem. , Hov.  1921 


1052 


' I. 


I 4 


k . . 

I ■ 


• 4 


'.t'v  ^ K. 

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A 

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t 

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fit'..:  fX:  ■ 'I'r  t 


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i 


-12- 


Determination  of  Sulphur 

Sulphur  was  determined  in  both  iron  and  steel  by  the  Bamber 
Method,  ?/hich  v/as  chosen  because  it  is  reputed  to  give  the  most 
accurate  results,  even  though  it  requires  slightly  more  time  than  \ 
the  various  volumetric  methods. 

Procedure:  Pive  grams  of  the  sample  was  dissolved  in  cone, 

nitric  acid,  and  after  being  completely  dissolved,  two  grams  of 
solid  potassium  nitrate  was  added  and  the  solution  evaporated  to 
dryness  on  the  water  bath.  The  residue  was  heated  to  redness,  and 
after  cooling,  60  cc  of  a one  per  cent  sodium  carbonate  solution 
was  added  and  heated  to  boiling.  The  solution  was  filtered  and  the 
precipitate  v/ashed  thoroughly  with  a one  per  cent  sodium  carbonate 
soliution.  The  resulting  filtrate  was  acidified  with  dilute  hydro- 
chloric acid  and  evaporated  to  dryness.  The  residue  was  moistened 
with  2 cc.  of  cone,  hydrochloric  acid  and  50  cc.  of  distilled  water 
added,  and  filtered.  The  filtrate  was  dilated  to  100  cc.  and  30  cc I 
of  a two  per  cent  barium  chloride  solution  added.  The  resulting 
precipitate,  barium  sulphate,  was  separated  by  filtration,  dried, 
ignited  and  weighed  in  the  usual  manner. 

The  resulting  precipitate  contains  13.85/^  sulphur  and  by 

knowing  the  weight  of  the  original  sample  the  per  cent  of  sulphur 
was  calculated. 

Determination  of  Phosphorous 
Preparation  of  Ammonium  Molybdate  Solution: 

Solution  1.  One  hundred  gwams  of  85^^  molybdic  acid  was  placed 


I 


in  a beaker  and  240  cc  of  v/ater  and  140  cc  of  aramoniuin  hydrozid^ 
solution,  d.  0.90,  added.  The  solution  was  filtered  and  60  cc  of 
cone,  nitric  acid  added. 

Solution  2.  400  cc  of  cone,  nitric  acid  and  960  cc  of  dis- 

tilled water  w'ere  mixed. 

When  solution  1 and  2 were  cooled,  solution  1 was 
added  to  solution  2 v/ith  constant  stirring.  Then  0.1  gr. 
of  aimnoniuin  phosphate  dissolved  in  10  cc  of  distilled  water 
was  added  with  constant  stirring  and  after  standing  for  24 
hours  the  resulting  solution  was  ready  for  use. 

Preparation  of  Magnesia  Mixture: 

Pifty  grams  of  anhydrous  magnesium  chloride  were  dissolved 
in  750  cc  of  distilled  water  and  then  150  cc  of  ammonium  hydroxide, 
d.o.  90,  was  added. 

Procedure:  Pive  grams  of  steel  was  weighed  into  an  Krlen- 

meyer  flask  and  dissolved  in  76  cc  of  cone,  nitric  acid.  The  re- 
sulting solution  was  heated  to  boiling  and  12  cc  of  strong  potass- 
ium permangate  v/as  added  and  boiling  continued  until  manganese 
dioxide  precipitated.  The  manganese  dioxide  precipitate  v;aS 
dissolved  by  the  addition  of  ammonium  bisulfite  solution,  an  ex- 
cess being  avoided.  The  resulting  solution  was  boiled  until  clear 
and  free  from  brovai  fumes.  The  solution  was  cooled  to  35  degrees 
C and  lOOcc  of  ammonium  molybdate  solution  added.  After  standing 

for  one  minute  the  solution  vms  shaken  for  three  minutes  and 
filtered.  The  precipitate  was  washed  three  times  v/ith  a two  per- 
cent nitric  acid  solution  to  free  it  from  iron.  Then  it  was 


-14- 


washed  I’idth  a ten  per  cent  solution  of  ammonium  hydroxide  and  the 
resulting  solution  allov/ed  to  run  into  a lOOoc  beaker  containing 
lOcc  of  cone,  hydrochloric  acid  and  0.5  gr.  of  citric  acid.  30cc  of 
cone,  ammonium  hydroxide  was  added  and  then  lOcc  of  the  magnesia 
mixture  added  very  slowly  xvith  constant  stirring.  After  two  hours 
the  solution  was  filtered  and  washed  v;ith  a ten  per  cent  ammonium 
hydroxide  solution*  The  precipitate  was  then  placed  in  a porcelain 
crucible,  ignited  and  weighed.  T^e  weighed  precipitate,  Mg2P207, 
contains  27.84  per  cent  phosphorous  and  from  this  value  the  per 
cent  of  phosphorous  in  the  original  sample  v;as  calculated. 


, I 


^IXPEHIISlITAi  WORK  . 


-15- 


All  the  samples  treated  were  melted  in  the  oil  pot  furnace 
situated  in  the  Assay  Laboratory.  This  furnace  had  an  outside 
diameter  of  about  three  feet  and  was  about  two  and  one  half  feet 
high.  The  furnace  v/as  heated  by  oil  forced  in  under  a gage  pres- 
sure of  about  tv/enty-five  pounds  and  mixed  with  a blast  of  air. 

If  was  possible  to  maintain  temperatures  ranging  from  thirteen  to 
fifteen  hundred  degrees  centigrade. 

The  molten  iron  or  steel  was  poured  into  a sand  mold  made 
by  pounding  moulding  sand  into  a crucible  about  twelve  inches  high  ■ 
and  five  inches  in  diameter  around  an  iron  bar  which  was  withdrawn 
af^er  the  mold  was  finished.  This  mold  was  then  dried  in  the 
electric  oven  at  a temperature  of  about  150  degrees  C.  for  several 
hours.  An  illustration  of  this  mold  is  shov/n  in  Eig,  2. 

In  order  to  prevent  oxidation  the  calcium  carbide  was  added 
in  covered  iron  crucibles.  These  crucibles  v;ere  made  of  sheet  iron 
and  were  about  two  inches  in  diameter  at  the  top  and  about  two 
inches  high.  The  cover  was  fastened  by  means  of  a piece  of  iron 
wire.  An  illustration  of  these  crucibles  is  shown  in  ^’ig.  3. 

In  test  No.  4 the  molten  iron  \vas  poured  from  the  crucible 
onto  a surface  of  calcium  carbide.  The  calcium  carbide  was 
sprinkled  over  a surface  of  sand  contained  in  a roasting  vessel 
constructed  of  a refractory  material.  An  illustration  of  this 
arrangement  is  shown  in  ^ig.  1. 

Drillings  for  analysis  were  obtained  by  means  of  a shaper 
in  the  University  of  Illinois  machine  shop. 


■"•"'j:  ■ -Hr  ^^Vv-xv  s u,','  i; 


- '7- 


•■^T'T  'W 

^*7^^  rn^ 


VI. j ’’M  ;. - 


: ' f 


I 


II 

r .Li' 

'5. 


■i'l'is  ■ >'.'t  'x*  * <’•■  rflfcr^T  » y-j.,dvr  fj  r 

t ' ' ■•  ^ *v*.  ' 

«■- M .Uu . HA  , 4‘'  UC  ' ' ^ 

- ' • ; J6|k  ■•  o iu-  \;'ii  is,n,j:it;i 

.►i  ir^  .--.ftT-' .'  . «!-.  i«^; .'tjoa^  Ort. 

^ . 1'.  ' ft  ;^' 

a»H7  r,  hi\T.;Sf:t  <y  • t..,  . i'</  f "ett  Ji. 

■ ,*  ^ ^ ■ 

*^  ■ t Ail  et)  c<9 


4RP  m 

W5^t,•l4ap^  1^  t^5  3A  <r^*r  : -o  rvoii 

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ji|^hi»-  A.O 


v-in  pi  ^ ^ 


ru':<  ,a«i  ^ ^ iWiij-.  ^ ; 

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’^€<1  •'311  .f*t>  tedlf  .*X  >’*  'i  *!V  , .6  loti  ll]S7 1 'X€?^f3t>V 


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dii\Jt  3^9 1**  i ' 'u  'i^voo  > 


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16 


^^^.3  /eov' 

Co/\/  y— ^ /^/ys/ cy  ^r^<c  O/i^/'-q 


-17- 


TEST, no.  1 

A ,38  carbon  steel  was  used  for  this  test  and  the  original 
was  mar  he  d Ho.  1 and  gave  the  follov/ing  analysis: 

Carbon-  - 0.38  io 
Phosphorous-  - 0.082;^ 

Sulphur-  - 0.038/0 

This  piece  v/as  melted  with  the  follov/ing  slag  in  the  oil  pot 
furnace.  Quantity  of  Steel — 1,000.0  gr. 


Ferrous  Phosphate  S»,0gr. 
Calcium  Fluoride  5.0 

Aluminim  Oxide  3.0 

Ferrous  Sulphide  28.0 

^alcium  Carbonate  10.0 

Silicon  di-oxide  22.0 


The  resulting  high  sulphur  and  phosphorous  content  sample  was 
poured  into  the  sand  mold  and  later  marked  lA,  Drillings  were 
obtained  and  gave  the  follov/ing  analysis; 

Carbon  0.57  io 

Phosphorous  0.711 
Sulphur  1,504 

This  high  sulphur  and  phosphorous  sample  marked  lA  was  placed 
in  a graphite  crucible  and  melted  v/ith  the  follov/ing  slag.  Twenty 
grams  of  calcium  carbide  were  added  directly  to  the  slag. 

Steel  500.0  gr 

Calcium  Carbonate-  10.0 
Calciimi  Fluoride  5,0 


-18- 


Alumintun  Oxide  3,0gr. 

Silicon  Dioxide  2E.0 
Calcium  Carbide  20.0 

After  heating  in  a molten  condition  in  the  oil  pot  furnace 
at  a temperature  of  about  1500  degrees  G,  for  one  hour,  the  metal 
was  poured  into  a sand  mold  and  allov/ed  to  cool  slo?/ly.  This 
sample  was  marhed  IB  and  drillings  were  obtained  and  analized  for 
carbon,  phosphorous  and  sulphur. 

The  following  analysis  was  obtained: 

Carbon  3.19  io 

Phosphorous  0.402 
Sulphur  1.10 

A comparison  of  the  composition  before  and  after  analysis 
follov/s : 


Barb on 

Phosphorous 

Sulphur 


Before  Treatment 
0.57  $ 

0.711 

1.304 


Per  cen$  Sulphur  Removed 
Per  cent  Phosphorous  Removed 


After  Treatment 
3.19  io 
0.402 
1.10 

16.69f^ 

43.60^ 


Conclusions:  This  test  shows  that  when  calcium  carbide  is  used  in 

large  amounts  there  is  great  danger  of  the  carbon  content 
increasing  excessiTely,  unless  very  high  tempreatures  are 
used  at  vhiich  the  carbide  will  not  decompose.  However,  the 
results  shov/  a decrease  in  the  sulphur  and  phosphorous  con- 
tent after  treatment  with  calcium  carbide. 


■J 

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-19- 


TSST  no.  2 

A sample  of  .38  carbon  steel  similar  to  that  used  in  test 
Ho.  1 was  used  for  this  test,  but  the  temperature  required  to  pro- 
duce the  desired  fluidity  of  thfe  metal  was  so  high  that  the  cruci- 
ble being  used  was  melted  and  the  charge  was  lost. 

Due  to  the  impossibility  of  obtaining  temperatures  high 
enough  to  produce  a molten  bath  of  the  desired  fluidity,  the  re- 
maining tests  were  made  on  cast  iron. 


-yf 

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p i: 


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• -'  ‘'v!^  '"  *^!i^ 

'’.\A  cj;*:c*1»'  4£^,  "'"-«  -i4>  ■ 

’'  ff iSI'J’ .^1) ’ . >rt lt> --I*  ■ iilvufladi^jtir  'r'fcN 
> , itu'  12-  .U’9  \A K ; f-  •»('•■* :f<'  V vf  ta9t rvd> , 4 

t '^'  "'  *1  W-,  /•  \lfL  ■ 

‘ ^ . '. . iMHi ' '« ^ ^ 


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s*  V tii! 


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-20- 

TEST  ITO.  3 

The  object  of  this  test  was  to  determine  what  effect  addit- 
ions of  calcium  carbide  and  ferrous  tiixide  with  no  other  slag- 
material  would  produce. 

A sample  of  cast  iron,  obtained  at  the  University  of  Illin- 
ois foundry,  was  used  for  this  test.  It  was  analyzed  for  carbon, 
phosphorous  and  sulphur  giving  the  follov/ing  results: 

Carbon  2,866/^ 

Phosphorous  0,552 
Sulphur  0,136 

Due  to  the  comparatively  high  content  of  sulphur  and  phos- 
phorous in  this  original  sample,  no  treatment  to  increase  the 
sulphur  and  phosphorous  content  was  required.  Therefore,  in  the 
tabulated  results  of  analysis  samples  No.  3 and  No.  SA  are  both 
listed  with  the  same  analysis. 

Sight  hundred  grams  of  this  sample  was  placed  in  a crucible 
and  heated  to  a molten  condition  in  the  oil  pot  furnace.  Then 
fifteen  gr.ams  of  ferrous  oxidd  and  twenty- five  grams  of  calcium 
carbide,  contained  in  a covered  iron  crucible  was  aiided.  Heating 
was  continued  and  thirty  minutes  later  the  crucible  was  removed 
from  the  furnace  and  the  molten  metal  was  poured  into  a sand  mold 
and  Etliowed  to  cool  slowly.  This  s£unple  was  marked  3B,  drillings 
obtained  and  an  analysis  made.  Results  of  analysis: 

Carbon  1,765% 

Phosphoroug  0.307 
Sulphur  0.129 


21- 


A comparision  of  the  analysis  "before  and  after  treatment  gave 


the  following  data: 
Carbon 
Phosphoroas 
Sulphur 


Before  Treatment 

0.552 

0.136 


After  Treatment 
1.765^ 

0.307 

0.129 

5.14/0 

44.38^ 


Per  cent  Sulphur  Removed 
Per  cent  Phosphorous  Removed 
Conclusions:  This  test  illustrates  that  phosphorous  removal  is  at 

a maximum  and  sulphur  removal  at  a minimum  when  metallic 
oxides  are  present. 

The  carbon  ibontent  of  the  iron  was  reduced  due  to  reaction 
V7ith  the  ferrous  oxide,  but  the  calcium  carbide  was  probably 
oxidized  to  lime,  which  caused  the  sulphur  content  to  be  reduced 
only  slightly,  due  to  the  oxidizing  conditions  present,  promoting 
the  reaction,  CaS  -i-  FeO  ^ PeS  -h  CaO, 


-E2- 


TE3T  ITO.  4 

The  object  of  this  test  was  to  determine  what  effect 
additions  of  calcimn  carbide  at  frequent  intervals  would  produce, 
i’urthermore , after  e^ch  addition  of  calcium  carlbide,  an  iddition 
of  calcimn  carbonate  was  made  with  the  object  of  producing  an 
agitation  of  the  molten  metal,  due  to  the  liberation  of  carbon 
dioside,  and  at  the  same  time  producing  a very  basic  slag.  This 
agitation  was  desired  so  that  a more  complete  reaction  between 
the  calcium  carbide  and  the  metal  would  be  possible. 

The  sample  of  cast  iron  used  in  this  test  was  obtained  at 
the  University  of  Illinois  foundry,  and  was  marhed  No,  4,  Drill- 
ings from  this  sample  were  obtained  and  an  analysis  made. 

Results  of  Analysis: 

Garb  on  3,46 

Phosphorous  0,440 
Sulphur  0, 087 

Then  the  sulphur  and  phosphorous  content  of  this  iron  was 
increased  by  treatment  with  the  follov/ing  slag  material: 


CO 

o 

phosphate 

26.0  gr 

Perrous 

sulphide 

28.0 

^alcium 

fluoride 

5.0 

Aluminum  oxide 

3.0 

Calcium 

carbonate 

5.0 

Silicon 

dioxide 

22. 0 

Quantity  of  cast  iron  treated  1300  gr. 

The  iron  was  melted  with  this  slag  material,  poured  into  a 


-23- 


mold,  and  allowed  to  cool.  After  cooling  the  sample  was  marked 
llo.  4A  and  drillings  were  obtained  and  analyzed, 

Hesults  of  analysis: 

Carbon  2,81  io 

Phosphorous  0,533 
Sulphur  0.408 

Phis  sample,  No.  4A,  then  received  the  following  treatment. 
1150  gr,  of  this  iron  was  placed  in  a graphite  crucible  and  the 
follov/ing  slag  material  was  added,  with  the  object  of  lowering  the 
sulphur  and  phosphorous  content. 


Calcium 

fluoride 

6.0  gr 

Aluminum  oxide 

3,0 

Calcium 

carbonate 

10.0 

Silicon 

dioxide 

22.0 

The  crucible  was  then  placed  in  the  pot  furnace  and  the 
contents  heated  to  a molten  condition.  Then  a covered  iron  cruciblei 
containing  35,0  grams  of  finely  gro'ind  calcium  carbide  v/as  dropped 
into  the  molten  metal  and  the  heating  at  a temperature  of  about 
1500  degrees  G,  continued.  Thirty  minutes  later  another  closed 
iron  crucible  containg  15,0  grams  of  calcium  carbide  was  added,  and 
this  addition  was  immediately  follov/ed  by  the  addition  of  twenty 
grams  of  calcium  carbonate  v/hich  itvas  also  contained  in  a closed 
iron  crucible. 

Thirty  minutes  later  fifteen  grams  more  of  calcium  carbide 
was  added  and  followed  by  the  aftftltlon  of  fifteen  grams  of  cal- 
cium carbonate.  Heating  at  a temperature  of  1500  degrees  C,  was 
continued  for  tv;enty  minutes,  and  the  crucible  was  then  removed 


I -j' 


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V*  J 


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2'  • y( . ' .4'  * ,* 


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-24- 


from  the  furnace  and  the  molten  metal  poui'ed  into  a sand  mold  and 
allowed  to  cool  slowly. 

This  sample  was  marked  Uo.  4B  and  an  analysis  made  giving  the 
follov/ing  results: 


Car h on  3,30  io 

Phosphorous  0.434 
Sulphur  0.272 

Before  Treatment 
Carbon  2.81^ 

Phosphorous  0,535 

Sulphur  0.408 

Percent  Sulphur  Hemoved 
Percent  Phosphorous  Kemoved 


After  Treatment 
3.30 
0.434 
0.272 

33.3  io 
18,57% 


Conclusions:  This  test  gave  a fairly  efficient  removal  of  sulphur 

and  phosphorous  and  removel  appears  to  be  more  complete  by 
use  of  this  method  than  by  any  of  the  previous  methods  tried. 

The  difficulty  of  maintainiiig  the  fluidity  of  a slag 
so  rich  in  lime  is  one  objection  to  this  type  of  procedure. 


fK  . 


1 


1 


(■ 


. r?- 


-85- 


TSST  HO,  5 

The  object  of  this  test  was  to  determine  the  possibilities 
of  sulphur  and  phosphorous  removal  by  first  treating  the  cast  iron 
v/ith  calcium  carbide  in  the  pot  furnace,  and  then  removing  it  irom 
the  furnace  and  pouring  it  over  a surface  covered  with  calcium 
carbide. 

Sample  Ho  4B  obtained  by  Test  Ho,  4 waa  treated  during  this 
teat.  The  composition  in  regard  to  carbon,  phosphorous  and  sulphur 
was  as  follows : 

Carbon  3,30  io 

Phosphorous  0,434 
Sulphur  0,272 

This  sample.  Ho,  4B,  was  placed  in  a graphite  crucible  and 
the  following  slag  material  added: 


Calcium  Pluoride 

10, 

,0 

gr. 

Aluminum  Oxide 

6, 

,0 

gr. 

Calcium  Carbonate 

20. 

,0 

gr. 

Silicon  dioxidd 

30. 

,0 

gr. 

Calcium  carbide 

20. 

.0 

gr. 

1670  grams  of  this  iron  v;as  placed  in  a crucible  and  cover- 
ed with  the  slag  material.  The  crucible  was  placed  in  the  pot 
furnace  and  heated  at  a temperature  of  about  1400  degrees  C,  for 
one  hour.  Then  the  crucible  was  removed  from  the  furnace  and  the 
contents  poured  over  a sui'face  of  calcium  carliide,  an  illustration 
of  which  is  shown  in  Pig,  1, 

The  molten  metal  solidified  on  this  surface  and  due  to  rapid 
cooling  was  brittle  enough  to  be  broken  into  piSiees,  These  pieces 


f 


« ' 


✓ 


'.oU 


'!i 


f ? ' '/.Lily' J'  . 


I 


-26- 


were  placed  in  a crucible  and  heated  to  a molten  state  and  then 
poured  into  a sand  mold* 

After  cooling  the  resulting  sample  was  marked  5B,  and 
analyzed  giving  the  follov/ing  results: 

Carbon  3.54  i<> 

Phosphorous  0*525 
Sulphur  0*120 

Before  Treatment  After  Treatment 


Carbon  5.30  > io 

Phosphorous  0*454  0*525 

Sulphur  0.272  0A20 

Per  cent  Sulphur  Hemoved  55* 88^ 

Per  cent  Phosphorous  Removed  25*11^ 


Conclusions:  This  method  of  treatment  gives  the  highest  removal 

of  sulphur  and  phosphorocro  and  seems  more  efficient  than 
any  of  the  other  methods  studied,  and  it  appears  that  the 
sulphur  and  phosphorous  content  of  the  metal  can  be  reduced 
by  allowing  the  metal  to  run  over  jealeium  carbide  as  it  is 
pouring  from  the  furnace* 


»*• 


y 


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T! 


A 


/ 


33SUtTS  OP  1ITALY3I3 

Test  No,  1 


Sample  No. 

1 

lA 

IB 

Garl)on 

0.38  $ 

0,57  $ 

3.19  $ 

PhospJioroas 

0,082 

0.711 

0.402 

Sulpiiur 

0.038 

1.504 

H 

. 

O 

Test  No.  3 


Sample  No, 

3 

3A 

3B 

Carbon 

2.866'^ 

2.866"/o 

1.765^ 

Pho sphorous 

0.552 

0.552 

0.307 

Sulphur 

0.136 

0.136 

U.129 

Test  No,  4 


Sample  No. 

4 

4A 

4B 

Carbon 

5,45  io 

2.61  1o 

3.30  1o 

Phosphorous 

0.440 

0. 533 

0.454 

Sulphur 

0.87 

0.408 

0.272 

Test  No,  5 


Sample  No, 

5 

5A 

5B 

Carbon 

3.50  io 

3.30  ^ 

5.34  °/o 

Phosphorous 

Q.434 

0.434 

0,325 

Sulphur 

Q.272 

0.272 

0.120 

4* 


f 


I 


/ 


: 'I 


-S8- 


SUMI.IARY 

OP  RESULTS 

Original  Solpliur  and 

Seduction  in  Sulphur 

Phosphorous 

Content 

And  Phosphorous  Content 

Test  Ho.  1 

Sulphur 

Phosphorous 

1.304^ 

0.7ir^ 

15.69  io 
43.60  1o 

Test  Ho.  2 

Discarded 

Discarded 

Test  Ho.  3 

Sulphur 

Phosphorous 

0.136/0 

0.65g‘/^ 

5.14  io 
44.38  i 

Test  Ho.  4 

Sulphur 

Phosphorous 

0.408^0 

0.533>b 

33.3  fo 
18.57  fo 

Test  Ho.  5 

Sulphur 

Phosphorous 

0.272^ 

0.434^ 

55.88  io 
25.11  io 

1 


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4 


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-E9- 


Summary : 

1.  V/hen  sulphur  removal  is  at  a iiAxlmum  then  phosphorous 
removal  is  at  a minimum,  and  vice  versa,  due  to  the  fact  that  re- 
ducing conditions  must  be  present  during  the  desulphurizing  period 
and  oxidizing  conditions  must  prevail  during  the  dephosphorizing 
period# 

2.  After  dephosphor ization  with  a slag  rich  in  lime  and 
metallic  oxides,  this  slag,  having  a high  content  of  3Ca(), 

should  be  removed  and  a slag  rich  in  lime  and  calcium  carbide  intro- 
duced into  the  furnace  during  the  desulphurizing  period* 

3.  During  the  dephosphorizing  period  comparatively  low 
temperatures  (l600  degrees  0, ) can  be  maintained,  but  during  the 
desulphurizing  period  very  high  temperatures  (2000  degrees  to 
2500  degrees  C, ) must  exist  so  that  the  desired  fluidity  of  the 
rich  lime  slag  will  be  possible  and  the  calcium  carbide  ?/ill  not 
decompose# 

4#  Electric  furnaces  are  the  only  type  of  furnace  capable 
of  producing  temperatures  high  enough  to  accomplish  complete  re- 
fining of  iron  and  steel,  but  because  of  the  cost  of  operation  are 
somewhat  prohibitive# 

5,  The  use  of  an  electric  furnace  in  conjunction  with  a Basi: 
Open  Hearth  furnace  or  Bessemer  Converter  appears  to  be  the  ideal 
type  of  process  for  producing  high  grade  steel# 


I'iU  JiM  ^ (£:  J L'7<';r  ' ' :*  “ifii 

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-30- 

Conclusions: 

The  fact  that  calcium  carbide  will  exist  only  at  very 
high  temperatures  makes  its  use  in  the  Basic  Open  Hearth  furnace 
impossible,  and  the  application  of  calcium  carbide  to  processes 
other  than  electric  furnace  processes  seems  to  be  a process  of 
desulphurization  and  dephosphorization  by  allowing  the  molten  metal 
to  run  over  calcium  carbide  as  it  lea'tes  the  furnace,  as  described 
in  Test  Ho.  6. 

Complete  desulphurizing  and  dephosphorizing  is  not  possible 
by  this  method  but  a considerable  reduction  of  the  content  of 
these  elements  is  effected  by  this  method. 

The  danger  of  increasing  the  carbon  content  excessively  in 
the  case  of  low  carbon  steels  is  present,  however,  high  carbon 
steel  and  cast  iron  could  bo  treated  in  this  manner. 


Suggestions  for  further  V^ork: 

1-  The  necessity  of  a furnace  capable  of  producing  temperatures 
of  at  least  2000  degrees  C cannot  be  too  greatly  emphasized  in  work 
of  this  character. 

2-  With  these  high  temperatures  the  importance  of  crucibles 
made  of  refractory  material  capable  of  withstanding  this  heat  also 
presents  itself. 

3-  A study  of  the  rate  of  desulphurization  and  dephosphorizat- 
ion with  variations  in  time  would  furnish  important  data. 


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-Sl- 


BIBLIOGRAPHY 

B.  Stoughton-  - - "The  Metallurgy  of  Iron  and  Steel." 

1903,  Published  by  McGraw-Hill  Book  Co.  | 

Hew  York,  Hew  York.  | 

1 

This  book  gives  a good  description  of  the  manufacture  and 
mechanical  treatment  of  steel  and  cast  iron.  It  also  con- 
tains much  information  upon  the  heat  treatment  of  steel,  and 
a discussion  of  alloy  steels. 

Hall  and  Williams  "The  Chemical  and  Me tallo graphic  Examination  of 

Iron,  Steel  and  Brass". 

19E1,  Published  by  McGraw-Hill  Book  Co. 

Hew  York,  H.  Y, 

It  is  from  this  book  that  the  methods  of  analysis  used  in 
this  thesis  work  were  taken,  and  this  book  gave  the  most 
complete  and  simple  analysis  method  for  every  element  in 
steel.  There  are  several  micro-photographs  shown  al  ong  with 
a complete  discussion  of  me tallo graphic  methods. 

k.  Bichmann-  - - "The  Basic  Open  Hearth  Process" 

1911,  Published  by  B.  VanHostrand  a Co. 

Hew  York,  H.  Y, 

This  bock,  written  by  a technical  man  gives  a good  des- 
cription of  the  Basic  Open  Hearth  Process  and  conditions  required 
for  maximum  .'emoval  of  sulphur  and  phosphorous. 

Camp  and  Prancis  "The  Making,  Shaping  and  Treating  of  Steel." 

1920,  Published  by  the  Carnegie  Steel  Co. 

, Pitt Sl->n-rp>,  Pa, 


% 


I 


.L 


O ! . 


. fru  - 


» * 

^ ' •- 

‘x*'' -U'7-^ 

, 

”l''  _ 

. A,-*  • 

* ^ . ; 

( '.  .. 

' 

’ , J.' 

'V  ., 

■ :i  XV'W-)  . ■ I-.' 

; .-'‘Vd  'V.- 

Xl. .’ 

1 • 

.;.^^U.:^  :- 

, • a.  •*. 

« 

, ; '“/••■  ■ V • 

. ..  ■ ■ Ji 

f 


:l> 


4*  t 


‘:oU 

" S'iv 

t..  ; 


• .0,.  i n 

iK'ii  .}.'< 


■ I.'.' 


> ;i  ;’'„ 


i 

, '(7.  JSift 


1 j..  , I 


{ ».. 


( ■ 


'M--  "Jii. 


• : lo  ,Xw 

' V . viv 


, : c^'4- 


.'■.1 ' 


.-••itijXi 


‘ ^tL 


uSV- 


A... 


.■  '»  i 


1. 


The  complete  desoription  of  the  manafacture  of  all  types 
of  steel  as  presented  in  this  hook  makes  this  hook  in- 
dispensihle  to  anyong’  interested  in  iron  and  steel. 


-28- 


C,  H,  ^’ulton  - "Principles  of  Metallurgy." 

1910,  Published  hy  the  McGraw-Hill  Co. 

Hew  York,  H.  Y. 

This  is  a very  good  hook  to  get  the  basic  principles  from 
on  the  solution  theory  of  carbon  and  iron,  as  well  as  some 
information  on  metallurgical  operations  in  general.  The 
information  obtained  from  this  book  combined  with  a further 
discussion  as  given  in  B.  Stoughton* s "Metallurgy  of  Iron 
and  Steel,"  should  make  the  solution  theory  very  simple. 


A,  Sauveur-  - "The  Metallography  and  Heat  Treatment  of  Iron  and 

Steel." 


1916,  Published  by  Sauveur  and  Boylston. 

Cambridge,  Ife,ss. 

This  book  gives  a complete  discussion  of  steel  in  regard  to 
its  various  elements,  heat  treatments,  and  Ifetallographic 
Methods,  along  v;ith  numerous  microphoto  graphs. 


Hodenhauser,  Schoenawa  and  ^om  Baur  "Electric  Pnrnaces  in  the  Iron 

and  Steel  industry. " 

1917,  Published  by  J.  V/iley  and  Sons,  Londo?'#  , Eng. 
A complete  description  of  the  manufacture  of  steel  in  elec- 
tric furnaces  is  given  in  this  book  with  special  reference 
to  the  slag  material  and  reactions. 


- 33. 


PERIODICALS 


Journal  of  the  Iron  and  Steel  Institute 

This  journal  contains  many  interesting  articles  pertaining 
to  iron  and  steel  among  vjhich  the  following  was  most  interes 
ing  and  appropriate  to  this  thesis. 

J.  0,  Arnold  and  G*  B.  Waterhouse-  - "The  Influence  of  Sul|ihur 
and  Manganese  on  Steel." 

Eo.  1 1903.  pp  136-160 


Journal  of  Ind.  and  Engineering  Chemistry 

This  journal  although  dealing  chiefly  with  chemical  re- 
ports often  contains  articles  an  metallurgy.  The  article  on 
an  ahsorhtion  tovirer  for  COg  was  especially  applicable  to 
this  work. 

"Sodium  Hydroxide  as  an  Absorbent  for  Carbon  Dioxide." 

Helly  and  Evers,  h'ov.  1921  page  1052 


Chemical  and  Metallurgical  Engineering. 

Several  articles  pertaining  to  this  work  were  found  in  this 
journal  among  which  the  following  were  most  important: 
"Deoxidation  and  Desulphurization  in  the  Heroult  Eurnace". 

E.  T.  Sisco  Jan.  4,  1922  pp  17-22 
"Desulphurizing  Cast  Iron" 

^lay  10.  1922  p 887 

Chemical  Abstracts. 

A summary  of  each  of  the  various  articles  presented  to  the 


-34- 

chemistry  field  is  given  in  this  puhlication  of  the  American 
Chemical  Society. 

The  abstract  of  an  article  entitled,  "The  De sulphur izdt- 
ion  and  Dephosphorization  of  Iron  and  Steel  by  Slags," 

14,  2151-52  1920,  was  of  special  interest. 

Journal  of  the  American  Chemical  Society. 

Several  articles  of  metallurgical  interest,  although  not 
pertaining  directly  to  this  v/ork  were  found  in  this  period- 
ical. 

The  following  periodicals  were  also  consulted: 

The  Iron  Age 

The  5’oundry 

The  Iron  Trade  Heviev/. 


UNIVERSITY  OF  ILLINOW-URBANA 


3 0' 

12 

101 

35 

1271 

•If 


